EP0753562B1 - Verfahren zur Umsetzung von Synthesegas in flüssiger Phase - Google Patents

Verfahren zur Umsetzung von Synthesegas in flüssiger Phase Download PDF

Info

Publication number
EP0753562B1
EP0753562B1 EP96401465A EP96401465A EP0753562B1 EP 0753562 B1 EP0753562 B1 EP 0753562B1 EP 96401465 A EP96401465 A EP 96401465A EP 96401465 A EP96401465 A EP 96401465A EP 0753562 B1 EP0753562 B1 EP 0753562B1
Authority
EP
European Patent Office
Prior art keywords
liquid phase
process according
hydrocarbons
synthesis gas
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96401465A
Other languages
English (en)
French (fr)
Other versions
EP0753562A1 (de
Inventor
Patrick Chaumette
Pierre Boucot
Pierre Galtier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP0753562A1 publication Critical patent/EP0753562A1/de
Application granted granted Critical
Publication of EP0753562B1 publication Critical patent/EP0753562B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/06—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen in the presence of organic compounds, e.g. hydrocarbons

Definitions

  • the present invention relates to a process for synthesizing essentially C 5 + hydrocarbons (that is to say hydrocarbons comprising at least 5 carbon atoms per molecule), usable as fuel or liquid fuel, from gases of synthesis.
  • the synthesis gas is a CO- (CO 2 ) -H 2 mixture, that is to say a CO-H 2 mixture of carbon monoxide (CO) and hydrogen (H 2 ) optionally comprising carbon dioxide carbon (CO 2 ).
  • the reaction for the synthesis of hydrocarbons from synthesis gas generally carried out at a temperature between 150 and 350 ° C. and under pressure, is known under the name of Fischer-Tropsch synthesis.
  • the catalysts usually used for the transformation of CO- (CO 2 ) -H 2 mixtures into liquid or gaseous hydrocarbons generally comprise at least one group VIII metal such as iron, ruthenium, cobalt or nickel.
  • the products prepared by Fischer-Tropsch synthesis in the presence of these metal catalysts have a very wide distribution in terms of molecular weight. Thus only a small proportion of the products obtained is in the range of middle distillates consisting of kerosene and diesel fractions, the kerosene fraction (s) being constituted by a mixture of hydrocarbons, the points of which boiling are approximately between 140 and 300 ° C, and the diesel fraction (s) being constituted (s) by a mixture of hydrocarbons whose boiling points are approximately between 180 and 370 ° C during 'An atmospheric distillation as carried out on a crude oil by the skilled person.
  • the reaction which it is sought to carry out in the context of the present application is the reaction for the synthesis of essentially C 5 + hydrocarbons from synthesis gas.
  • the Fischer-Tropsch synthesis is a very exothermic reaction. So when the process for carrying out said synthesis reaction is carried out in gas phase and with a fixed bed catalyst, the conversion of carbon must be limited below 85%, in order to avoid thermal instabilities in the catalytic bed, which forces to separate and recycle the synthesis gas not converted.
  • Another process which has been envisaged for carrying out the reaction consists in operate in the presence of a liquid phase and with a catalyst in suspension (circulating bed reactor also called “slurry"). In this case, the CO conversion can reach or even exceed 95%. On the other hand, the catalyst suspended and circulating with the inert liquid, must be separated from the reaction products, then recycled.
  • the object of the present invention is to provide a process which avoids the disadvantages of fixed bed / gas phase and circulating bed processes, and which makes it possible to preserve the advantages of a fixed bed reactor with downward flows of the liquid and the gas, while more particularly favoring the formation of C 5 + hydrocarbons compared to the formation of methane.
  • the process of the present invention is a process for synthesizing essentially linear and saturated C 5 + hydrocarbons from synthesis gas, the reactive gas phase flowing either in the downward direction or in the upward direction through a reaction zone comprising a fixed catalyst bed, said method being characterized in that it comprises the upward circulation through said zone of an inert liquid phase, with a surface speed greater than 0.01 cm / s, preferably greater than 0, 1 cm / s and even more preferably greater than 1 cm / s.
  • the method according to the invention is also called "trickle bed upflow".
  • the surface velocity of the inert liquid phase is defined as the ratio between hourly space velocity, under temperature and pressure conditions selected for the reaction, and the cross-sectional area of the area reaction zone, said zone being considered without catalyst.
  • Surface speed optimal depends in part on the size of the catalyst particles and the properties physico-chemical of the liquid. It seems practically independent of speed gas surface.
  • the reaction zone comprises one or more reactors, each reactor comprising at least one fixed bed of catalyst. In case the reaction zone includes several reactors, these can be placed in series or in parallel. In all cases, the configuration of the reaction zone is carried out in a good manner. known to those skilled in the art.
  • the catalyst particles generally have an average diameter of between 0.2 and 10 mm, preferably between 0.5 to 6 mm and more preferably between 1 and 3 mm.
  • the catalyst can be any type of catalyst effective in the synthesis reaction of hydrocarbons from synthesis gas.
  • any catalyst based on supported or unsupported iron or cobalt such as those described in the patent application European EP-A-0.581.619 and in French patent FR-A-2,677,992.
  • the liquid phase does not take part in the reaction and has no harmful effect on this last. It is preferably a hydrocarbon cut, again more preferred comprising essentially between 10 and 20 carbon atoms per molecule, such as a diesel cut or a kerosene cut. If the catalyst is sensitive to sulfur, a desulfurized hydrocarbon fraction is preferably used.
  • the liquid phase is preferably partially vaporizable in the reaction conditions, so as to eliminate the calories released by the reaction.
  • the liquid phase comprises at least minus a partially vaporizable product, for example between 0 and 80% of a product at least partially vaporizable. So calorie evacuations and transfers heat within the reaction zone are improved. We hear by 'vaporizable' any liquid product which, under the conditions of the reaction, is practically completely in the form of gas. 'Partially produced' means vaporizable 'a product of which a part, generally between 10 and 100%, is vaporizable.
  • the liquid phase includes a partially vaporizable hydrocarbon fraction, by example a hydrocarbon cut comprising hydrocarbons containing 5, 6, 7, 8, 9 or 10 carbon atoms per molecule.
  • the inert liquid phase is advantageously obtained by recycling part of a fraction of the hydrocarbons produced by the reaction; of preferably said fraction is the diesel or kerosene fraction of hydrocarbons produced by the reaction.
  • the inert liquid phase which is introduced initially in the reaction zone is brought in from the outside (as opposed to a liquid phase produced in the Fischer-Tropsch reaction zone, that is to say at the interior), then said liquid phase comprises part of a fraction of the hydrocarbons produced by the reaction which is recycled in said zone.
  • said fraction is the diesel fraction or the kerosene fraction.
  • the inert liquid phase generally has a density between 0.2 and 2.5 g / cm 3 and a viscosity between 0.05 and 10 centipoise (0.05 to 10 mPa.s) under the conditions of reaction, but these values are by no means mandatory.
  • the process according to the invention is particularly well suited to be used as a process for manufacturing from a synthesis gas a mixture of essentially linear and saturated hydrocarbons, generally containing at least 80% by weight, relative to all of the hydrocarbons formed, of a cut comprising C 5 + hydrocarbons and preferably less than 10% by weight of olefins in said C 5 + cut.
  • the process according to the invention therefore makes it possible to obtain essentially paraffinic hydrocarbons, the fraction of which exhibiting the highest boiling points can be converted with a high yield into middle distillates (diesel and kerosene cuts) by a hydroconversion process. such as hydrocracking and / or catalytic hydroisomerization (s).
  • the conversion of synthesis gas to hydrocarbons is generally carried out under a total pressure between 0.1 and 15 MPa, preferably between 0.5 and 10 MPa, the temperature being between 150 and 350 ° C, preferably between 180 and 270 ° C.
  • Hourly volume velocity is usually between 100 and 20,000 volumes of synthesis gas per volume of catalyst and per hour and preferably between 400 and 10,000 volumes of synthesis gas per volume of catalyst and per hour.
  • the H 2 / CO molar ratio in the synthesis gas is generally between 0.5 and 5, preferably between 1.2 and 3.5.
  • the catalyst is first of all loaded into the reaction zone and prereduced by contacting at least one reducing compound, for example pure hydrogen or a mixture of reducing gases such as hydrogen and / or carbon monoxide, and optionally at least one inert gas such as nitrogen, molar ratio (reducing compound) :( compound reducing agent + inert gas) being between 0.001: 1 and 100: 1 in the case where at least an inert gas is present.
  • Pre-reduction is generally carried out between 150 and 600 ° C, preferably between 200 and 500 ° C, between 0.1 and 10 MPa, and at a speed hourly volumetric from 100 to 40,000 volumes of mixture per volume of catalyst per hour.
  • This pre-reduction is possibly carried out in phase liquid, the liquid phase of the prereduction being for example made up of at least a hydrocarbon comprising at least 5 carbon atoms per molecule.
  • the catalyst used in Examples 1 to 4 is prepared as follows:
  • the gel obtained is separated from the mother liquors by filtration, washed with water, dried in an oven. between 40 and 120 ° C, then calcined at 450 ° C and shaped by tableting. the pastilles 5x5mm in size are then recalcined at 600 ° C.
  • the catalyst is reduced in the reactor, prior to synthesis of hydrocarbons, by means of a mixture containing 6% of hydrogen in nitrogen, up to 240 ° C, then with pure hydrogen up to 500 ° C, at pressure atmospheric.
  • Example 1 (according to the invention):
  • the synthesis gas (mixture H 2 + CO, line 1) and the liquid phase (line 2 ) flow from bottom to top and pass through 1.2 dm3 of the catalyst ( 3 ) mentioned. above and placed in a fixed bed in reactor 4 .
  • the liquid is distributed uniformly through a perforated plate ( 5 ).
  • the effluent is discharged by means of the pipe ( 6 ).
  • the liquid paraffins are separated from the gas phase, at the outlet of the reactor, in the separator ( 7 ), and sent continuously by the line ( 8 ) to the heater ( 10 ), up to the separator 11 .
  • the gas from the separator 7 is removed by means of line 9 and analyzed by chromatography.
  • the heavy paraffins synthesized in the reactor 4 are separated and then recovered via line 13 ; they are analyzed by chromatography.
  • a gaseous phase is recovered which, after passing through condenser 14 , condenses into the liquid phase recycled to reactor 4 via pump 15 and line 2 .
  • the reactor has a diameter of 4 cm and a height of 1 meter.
  • the synthesis gas used for the synthesis of hydrocarbons consists of a mixture containing 66.7% of hydrogen and 33.3% of carbon monoxide.
  • the gas is introduced with a flow rate of 1.2 m 3 / h, i.e. a gas VVH (hourly volume speed) of 1000 h -1 .
  • the reaction is carried out at 220 ° C and 2MPa.
  • the liquid phase is a C 10 -C 16 paraffin cut containing no sulfur which is introduced at the start of the unit, then separated from the effluents at the outlet of the reactor, and then recycled.
  • the flow rate of this liquid phase is approximately 200 l / h at the reaction temperature, ie a space speed of 4.5 cm / s. Products lighter or heavier than this liquid phase, as well as the water co-produced in the reaction, are separated, evacuated and analyzed.
  • C1, C2, C3, ... Cn the number of gram-molecules of carbon monoxide CO and carbon dioxide CO 2 (if CO 2 is present) transformed into hydrocarbons containing from 1 to n atoms of carbon per molecule;
  • the conversion is 72%
  • the selectivity for methane is 8%
  • the selectivity for C 5 + hydrocarbons is 86%.
  • the reaction is carried out under conditions identical to those of Example 1 except for the space velocity of the liquid phase which is 1 cm / s.
  • the reaction is carried out under conditions identical to those of Example 1 except for the gas phase which circulates from top to bottom with the same VVH equal to 1000 h-1.
  • the synthesis gas (mixture H 2 + CO, line 1) flows from top to bottom and the liquid phase (line 2 ) flows from bottom to top; the two phases pass through 1.2 dm3 of the catalyst ( 3 ) mentioned above and placed in a fixed bed in the reactor 4 .
  • the other references of FIG. 2 are those of FIG. 1.
  • the reaction is carried out under conditions identical to those of Example 1 except for the liquid and gas phases which both flow from top to bottom.
  • the synthesis gas (mixture H 2 + CO, line 1 ) and the liquid phase (line 2 ) both flow from top to bottom and pass through 1.2 dm3 of the catalyst ( 3 ) mentioned above and placed in a fixed bed in reactor 4 .
  • the other references of FIG. 3 are those of FIG. 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Catalysts (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Claims (10)

  1. Verfahren zur Synthese von im wesentlichen linearen und gesättigten C5+ Kohlenwasserstoffen, ausgehend von Synthesegas, wobei die reaktive gasförmige Phase entweder in absteigender Richtung oder in aufsteigender Richtung durch eine Reaktionszone zirkuliert, die wenigstens ein festes Katalysatorbett umfaßt, wobei das Verfahren sich dadurch auszeichnet, daß es die aufsteigende Zirkulation durch diese Zone einer flüssigen inerten Phase mit einer Oberflächengeschwindigkeit oberhalb 0,01 cm/s umfaßt.
  2. Verfahren nach Anspruch 1, derart, daß die Katalysatorpartikel einen mittleren Durchmesser zwischen 0,2 und 10 mm haben.
  3. Verfahren nach einem der Ansprüche 1 oder 2, derart, daß die flüssige Phase eine kohlenwasserstoffhaltige Fraktion ist.
  4. Verfahren nach Anspruch 3, derart, daß die Fraktion im wesentlichen Kohlenwasserstoffe mit 10 bis 20 Kohlenstoffatomen pro Molekül umfaßt.
  5. Verfahren nach einem der Ansprüche 1 bis 4, derart, daß die flüssige Phase eine Gasölfraktion oder eine Kerosinfraktion ist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, derart, daß die flüssige Phase wenigstens ein teilweise verdampfbares Produkt umfaßt.
  7. Verfahren nach Anspruch 6, derart, daß die flüssige Phase eine kohlenwasserstoffhaltige Fraktion umfaßt, welche Kohlenwasserstoffe umfaßt, die 5, 6, 7, 8, 9 oder 10 Kohlenstoffatome pro Molekül enthalten.
  8. Verfahren nach einem der Ansprüche 1 bis 7, derart, daß die Umwandlung des Synthesegases in Kohlenwasserstoffe unter einem Gesamtdruck zwischen 0,1 und 15 MPa durchgeführt wird, die Temperatur zwischen 150 und 350°C liegt, die stündliche Volumengeschwindigkeit zwischen 100 und 20000 Volumenteilen Synthesegas pro Volumenteile Katalysator und Stunde beträgt und das Molverhältnis H2/CO im Synthesegas zwischen 0,5 und 5 liegt.
  9. Verfahren nach einem der Ansprüche 1 bis 8, derart, daß der Katalysator vorher mitten in der Reaktionszone vorreduziert wird.
  10. Verfahren nach einem der Ansprüche 1 bis 9, derart, daß die flüssige inerte Phase erhalten wird, indem man einen Teil einer Fraktion der durch die Reaktion erzeugten Kohlenwasserstoffe recycliert.
EP96401465A 1995-07-13 1996-07-03 Verfahren zur Umsetzung von Synthesegas in flüssiger Phase Expired - Lifetime EP0753562B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8600037 1995-07-13
FR9508637A FR2736650B1 (fr) 1995-07-13 1995-07-13 Procede de conversion du gaz de synthese en phase liquide

Publications (2)

Publication Number Publication Date
EP0753562A1 EP0753562A1 (de) 1997-01-15
EP0753562B1 true EP0753562B1 (de) 1999-12-15

Family

ID=9481062

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96401465A Expired - Lifetime EP0753562B1 (de) 1995-07-13 1996-07-03 Verfahren zur Umsetzung von Synthesegas in flüssiger Phase

Country Status (8)

Country Link
US (1) US5786393A (de)
EP (1) EP0753562B1 (de)
DE (1) DE69605607T2 (de)
FR (1) FR2736650B1 (de)
MY (1) MY112375A (de)
NO (1) NO314697B1 (de)
SA (1) SA96170191B1 (de)
ZA (1) ZA965836B (de)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6616909B1 (en) * 1998-07-27 2003-09-09 Battelle Memorial Institute Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
AU2043400A (en) 1998-12-07 2000-06-26 Syntroleum Corporation Structured fischer-tropsch catalyst system and method for its application
US6451864B1 (en) * 1999-08-17 2002-09-17 Battelle Memorial Institute Catalyst structure and method of Fischer-Tropsch synthesis
DE60024462T2 (de) * 1999-08-17 2006-08-17 Battelle Memorial Institute, Richland Katalysatorstruktur und Verfahren zur Fischer-Tropsch-Synthese
BR0216052B1 (pt) * 2001-12-05 2012-12-11 planta gás para lìquido para processar metano e processo para processar metano.
GB0129054D0 (en) * 2001-12-05 2002-01-23 Accentus Plc Catalytic reactor and process
RU2210432C1 (ru) * 2001-12-21 2003-08-20 Институт катализа им. Г.К. Борескова СО РАН Катализатор и способ получения углеводородов и их кислородсодержащих производных из синтез-газа
US7232848B2 (en) * 2002-09-09 2007-06-19 Conocophillips Company Gas agitated multiphase reactor with stationary catalyst solid phase
MY139252A (en) * 2004-10-04 2009-09-30 Shell Int Research Catalyst structure
CN101275080B (zh) * 2008-05-19 2012-11-14 中国科学院山西煤炭化学研究所 一种基于固定床反应器的费托合成反应工艺
CN101307245B (zh) * 2008-05-19 2012-08-22 中国科学院山西煤炭化学研究所 一种利用固定床装置进行费托合成反应的工艺及设备
CN101928194B (zh) * 2009-06-18 2013-06-05 中国石油化工股份有限公司 一种固定床费托合成的方法
CN102211002B (zh) * 2010-04-12 2013-03-27 中科合成油技术有限公司 一种热油循环和冷激式固定床费托合成反应器及其应用
CN103691369B (zh) * 2013-12-09 2015-10-28 中国科学院山西煤炭化学研究所 一种基于固定床反应器的费托合成工艺
CN103695024B (zh) * 2013-12-09 2016-01-27 中国科学院山西煤炭化学研究所 一种适用于滴流床反应器的费托合成工艺
CN108579639B (zh) * 2018-04-03 2024-01-30 浙江新和成股份有限公司 一种制备氧代异佛尔酮的装置及方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE897549C (de) * 1939-04-01 1953-11-23 Basf Ag Verfahren zur katalytischen Umsetzung von Kohlenoxyd mit Wasserstoff zu Kohlenwasserstoffen
GB728543A (en) * 1952-03-05 1955-04-20 Koppers Gmbh Heinrich Process for the synthesis of hydrocarbons
NL7708307A (en) * 1977-07-27 1979-01-30 Shell Int Research Fischer-Tropsch hydrocarbon synthesis - using catalyst contg. ruthenium and iron-group metal
FR2494682A1 (fr) * 1980-11-25 1982-05-28 Inst Francais Du Petrole Procede pour la mise en oeuvre de reactions tres exothermiques
IN166813B (de) * 1985-01-18 1990-07-21 Shell Int Research

Also Published As

Publication number Publication date
SA96170191B1 (ar) 2006-04-22
DE69605607D1 (de) 2000-01-20
MY112375A (en) 2001-05-31
DE69605607T2 (de) 2000-04-13
EP0753562A1 (de) 1997-01-15
FR2736650B1 (fr) 1997-09-05
US5786393A (en) 1998-07-28
NO314697B1 (no) 2003-05-05
NO962930L (no) 1997-01-14
FR2736650A1 (fr) 1997-01-17
NO962930D0 (no) 1996-07-12
ZA965836B (en) 1998-01-12

Similar Documents

Publication Publication Date Title
EP0753562B1 (de) Verfahren zur Umsetzung von Synthesegas in flüssiger Phase
EP0245124B1 (de) Kombiniertes Verfahren für Hydroreformierung und Hydroisomerisierung
EP0820806B1 (de) Verfahren mit einer Gas-Flüssig-Blasenkolonne und Anwendung zu einer Fischer-Tropsch Synthese
US7226954B2 (en) Integrated process and apparatus for producing liquid fuels
US4423265A (en) Process for snygas conversions to liquid hydrocarbon products
CA1252801A (fr) Procede de conversion de methanol ou de dimethylether en olefines
US4471145A (en) Process for syngas conversions to liquid hydrocarbon products utilizing zeolite Beta
US2736684A (en) Reforming process
JPH0581635B2 (de)
FR2741064A1 (fr) Procede de conversion de gaz de synthese en hydrocarbures
EP0794239B1 (de) Umwandlung von Synthesegas in Kohlenwasserstoffe in Anwesenheit einer flüssigen Fase
BE1006675A3 (fr) Procede de production d'essences a haut indice d'octane.
EP0679709B1 (de) Verfahren zur Umsetzung von Erdgas zu Kohlenwasserstoffen
EP1448749A1 (de) Verfahren zur umwandlung in serien-reaktoren
EP1094049B1 (de) Verfahren zur Synthese von Kohlenwasserstoffen aus Synthesegas in Gegenwart von einer, in einer flüssigen Phase dispergierten Raney Metalllegierung
EP0240480B1 (de) Verfahren zur Behandlung von Kohlenwasserstoffen mit durch Halogenisierung stabilisierten Katalysatoren aus der Silicalit-oder TEA-Silikatreihe
JP2004532322A (ja) 蒸留液燃料範囲における炭化水素のフィッシャー−トロプシュ合成の最適化方法
FR2536759A1 (fr) Procede d'hydrogenation selective de dienes dans l'essence de pyrolyse
FR2802919A1 (fr) Procede et dispositif pour l'alkylation de l'isobutane par des olefines legeres
JP4126100B2 (ja) 触媒寿命が延長されたスラリー炭化水素合成方法
FR2832415A1 (fr) Procede de conversion de gaz de synthese dans des reacteurs en serie
JPS63156890A (ja) 炭素質物質の生成を抑制した重質油の軽質化方法
BE734902A (de)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE GB IT NL

17P Request for examination filed

Effective date: 19970715

17Q First examination report despatched

Effective date: 19980928

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

ITF It: translation for a ep patent filed

Owner name: DE DOMINICIS & MAYER S.R.L.

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE GB IT NL

REF Corresponds to:

Ref document number: 69605607

Country of ref document: DE

Date of ref document: 20000120

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20000114

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20100723

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20100721

Year of fee payment: 15

Ref country code: DE

Payment date: 20100816

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20100721

Year of fee payment: 15

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 69605607

Country of ref document: DE

Owner name: IFP ENERGIES NOUVELLES, FR

Free format text: FORMER OWNER: INSTITUT FRANCAIS DU PETROLE, RUEIL-MALMAISON, HAUTS-DE-SEINE, FR

Effective date: 20110331

Ref country code: DE

Ref legal event code: R081

Ref document number: 69605607

Country of ref document: DE

Owner name: IFP ENERGIES NOUVELLES, FR

Free format text: FORMER OWNER: INSTITUT FRANCAIS DU PETROLE, RUEIL-MALMAISON, FR

Effective date: 20110331

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20120201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20110703

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120201

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69605607

Country of ref document: DE

Effective date: 20120201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120201

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110703

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110703